CN111051461A - Dual cure adhesive compositions and methods of making and using the same - Google Patents

Abstract

Dual cure (condensation and free radical reaction) adhesive compositions are disclosed that are useful in electronic device applications.

Description

Dual cure adhesive compositions and methods of making and using the same

Cross reference to related patent applications

According to 35 u.s.c. § 119(e), the present application claims priority to us provisional patent application No. 62/548558 filed 8/22 in 2017. U.S. provisional patent application No. 62/548558 is hereby incorporated by reference.

Technical Field

The invention discloses an adhesive composition. The adhesive composition has a dual (free radical and condensation) cure system. The adhesive composition comprises a cluster functional polyorganosiloxane and a polyalkoxy functional polyorganosiloxane starting material.

Background

(meth) acrylic free radical curable compositions generally have the following disadvantages: the mass solidifies faster than the surface to the air, which results in an uncured or undercured liquid layer. It is believed that the potential mechanism is that oxygen in the air can quench the propagation of free radicals, resulting in a physical delay in crosslinking on the surface. Generally, polymeric (meth) acrylates may be more susceptible to oxygen inhibition than small molecule (meth) acrylates. Compared to methacrylates, acrylates may be more prone to oxygen inhibition.

Commercially available (meth) acrylic adhesives may be cured using silanol condensation to mitigate oxygen inhibition. Dual cure systems have been proposed which include both free radical cure and silanol-based condensation cure. In this system, the oxygen inhibition is reduced to some extent, but is still unsatisfactory. To introduce alkoxysilyl groups, the condensation cure component comprises a silicone resin treated with trimethoxysilylethyltetramethyldisiloxane (also known as ETM converter).

In the reaction scheme shown below, hydrosilylation reaction of vinyltrimethoxysilane with 1, 1, 3, 3-tetramethyldisiloxane using a platinum catalyst produces an ETM converter as a mixture comprising α -adduct branched isomer and β -adduct linear isomer as reaction products.

However, this process suffers from the disadvantage of selectivity resulting in a 65/35 molar ratio of β -adduct/α -adduct, furthermore, without immediate removal or deactivation of the Pt catalyst, a "hydrosilylation" will occur, resulting in a by-product (i.e., αα adduct, αβ adduct, βα adduct and/or ββ adduct) in which two hydrogen atoms on the hydrogen-terminated organosiloxane oligomer react with the vinyltrimethoxysilane molecule.

Adhesives comprising silicone resins and polymers end-capped with ETM converters prepared by the above-described route still exhibit unsatisfactory surface wetting and/or cure rates in some applications. There is a need in the industry for improved adhesive compositions that cure to form adhesives with faster cure speeds, improved surface cure, or both.

Disclosure of Invention

An adhesive composition comprising:

A) a poly (meth) acrylate cluster functional polyorganosiloxane,

B) a polyalkoxy-terminated resinous polymer blend,

C) a condensation reaction catalyst, and

D) a free radical initiator.

Detailed Description

Raw material A)

In the above adhesive composition, A) a poly (meth) acrylate cluster functional polyorganosiloxane comprising units of the formula: (R)₂R¹SiO_1/2)_aa(RR¹SiO_2/2)_bb(R₂SiO_2/2)_cc(RSiO_3/2)_dd(SiO_4/2)_ee((R_ff)O_{(3-ff)/ 2}SiD¹SiR_ffO_(3-ff)/2)_ggWherein each D¹Independently represent a divalent hydrocarbon group having 2 to 18 carbon atoms; each R independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 18 carbon atoms, each R¹Independently represents a methacryloyl-functional alkyl group or an acryloyl-functional alkyl group, subscript aa ≥ 0, subscript bb ≥ 0, amount (aa + bb) ≥ 4, subscript cc > 0, subscript dd ≥ 0, subscript ee ≥ 0, subscript ff 0, 1, or 2, and subscript gg ≥ 2.

Each R is independently a monovalent hydrocarbon group (as defined below) or a monovalent halogenated hydrocarbon group (as defined below). The monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group may have 1 to 18 carbon atoms. Suitable monovalent hydrocarbon groups for R include, but are not limited to, alkyl groups and aryl groups. Examples of suitable alkyl groups are methyl, ethyl, propyl, butyl and hexyl. Examples of suitable aryl groups are phenyl, tolyl, xylyl and phenyl-methyl.

Each R¹Independently represents a methacryloyl-functional alkyl group or an acryloyl-functional alkyl group. Is suitable for R¹Include methyl methacrylate, methyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate.

Each D¹Independently represents a divalent hydrocarbon group having 2 to 18 carbon atoms. Alternatively, each D¹May be selected from alkylene groups such as ethylene or propylene, arylene groups such as phenylene or aralkylene. Alternatively, each D¹May be an alkylene group such as ethylene or propylene.

In the above unit formulas, subscript aa is not less than 0, subscript bb is not less than 0, amount (aa + bb) is not less than 4, subscript cc is more than 0, subscript dd is not less than 0, subscript ee is not less than 0, subscript ff is 0, 1 or 2, and subscript gg is not less than 2. Alternatively, the amount (aa + bb) may be ≧ 6. Alternatively, the amount (aa + bb) may be ≧ 8. By the term "poly (meth) acrylate-clustered functional siloxane" is meant a siloxane having a linear or branched siloxane backbone structure and methacrylate or acrylate functional groups present in spatial proximity to each other in the terminal and/or side chain positions of the siloxane. The siloxane has a total of at least 4 methacrylate plus acrylate functional groups, and at least two of them are in close proximity to each other, i.e., they are "clustered".

Alternatively, a) the poly (meth) acrylate cluster functional polyorganosiloxane may have the formula:

r, R therein¹And D¹As described above. Subscript j is 0 to 2,000,000, and each subscript k is independently 1 to 12 (i.e., such that each ring has 4 to 15 silicon atoms). Alternatively, subscript j is 5 to 500,000, alternatively 5 to 100,00050,000, alternatively 10 to 10,000, alternatively 10 to 5,000, alternatively 20 to 2,000. Alternatively, subscript k is 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 to 2, alternatively k ═ 1. Alternatively, a) the poly (meth) acrylate cluster functional polyorganosiloxane may have the formula:

r, R therein¹、D¹And subscripts j and k are as described above.

The poly (meth) acrylate cluster functional polyorganosiloxanes can be prepared by known methods, such as disclosed in U.S. patent application publication 2016/0009865. The poly (meth) acrylate cluster functional polyorganosiloxanes for use herein may be the hydrosilylation reaction product of starting materials comprising:

a) a polyorganosiloxane having an average of at least two silicon-bonded aliphatic unsaturated groups per molecule;

b) an organohydrogensiloxane having an average of 4 to 15 silicon atoms per molecule, wherein the starting material b) has silicon-bonded hydrogen atoms;

with the proviso that the molar ratio of aliphatically unsaturated groups in starting material a) to silicon-bonded hydrogen atoms in starting material b) is from 1: 3 to 1: 20; and

c) a reactive species having at least one aliphatic unsaturated group and one or more free radical curable groups per molecule selected from acrylate functional groups and methacrylate functional groups.

Raw material B)

The starting material B) in the above adhesive composition is a polyalkoxy-terminated resin polymer blend. The polyalkoxy-terminated resin polymer blend comprises the reaction product of:

i) comprising the formula (R)^2' ₃SiO_1/2) And (SiO)_4/2) The siloxane resin of (a), wherein each R is^2’Independently a monovalent hydrocarbon group, provided that at least one R2' has a terminal aliphatic group per moleculeSaturated group, wherein the siloxane resin has (R)^2' ₃SiO_1/2) Units (M units) and (SiO)_4/2) The molar ratio of units (Q units) is in the range of 0.5: 1 to 1.5: 1 (M: Q ratio),

ii) comprises the formula (R)^2’ ₃SiO_1/2)_iiAnd (R)₂SiO_2/2)_hhWherein subscript hh is 20 to 1000 and subscript ii has an average value of 2, and

iii) an alkoxy-functional organohydrogensiloxane oligomer, said alkoxy-functional organohydrogensiloxane oligomer having the unit formula:

wherein R and D¹As mentioned above, each R³Independently is a monovalent hydrocarbon group as described above for R, subscript b is 0 or 1, subscript c is 0, subscripts f, h, i, and k have values such that 5 ≧ f ≧ 0, 5 ≧ h ≧ 0, subscript i is 0 or 1, subscript kk is 0 or 1, subscript m > 0, and an amount (m + n + f + o + h + i + p + kk) of ≦ 50, provided that > 90 mole% of all D groups in the capping agent are linear; and

iv) a hydrosilylation reaction catalyst.

Raw material i)

The silicone resins used for preparing the starting materials B) were: i) comprising the formula (R)^2' ₃SiO_1/2) And (SiO)_4/2) The siloxane resin of (a), wherein each R is^2’Independently a monovalent hydrocarbon group, with the proviso that at least one R2' has a terminal aliphatic unsaturated group per molecule, wherein the silicone resin has (R^2’ ₃SiO_1/2) Units (M units) and (SiO)_4/2) The molar ratio of units (Q units) is in the range of 0.5: 1 to 1.5: 1 (M: Q ratio), and the starting material i) may comprise an average of 3 to 30 mole%, alternatively 0.1 to 5 mole%, alternatively 3 to 100 mole% of aliphatic unsaturation. For R^2’The aliphatically unsaturated group of (a) may have 2 to 18 carbon atoms. For R^2’The aliphatically unsaturated group of (a) can be an alkenyl group, an alkynyl group, or a combination thereof. The mole% of aliphatic unsaturation in the silicone resin is the ratio of the number of moles of unsaturated group-containing siloxane units in the resin to the total number of moles of siloxane units in the resin multiplied by 100. For R^2’The remaining monovalent hydrocarbon groups of (a) can be, for example, alkyl or aryl groups having 1 to 18 carbon atoms.

Methods of preparing resins are known in the art. For example, the resin may be prepared by treating a resin copolymer produced by the silica hydrosol endcapping process described by Daudt et al with at least one alkenyl-containing endcapping agent. The process described by Daudt et al is disclosed in U.S. Pat. No. 2,676,182.

The method of Daudt et al involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane (such as trimethylchlorosilane), a siloxane (such as hexamethyldisiloxane), or a mixture thereof, and recovering a copolymer having M units and Q units. The resulting copolymer typically contains from 2 to 5 weight percent hydroxyl groups.

The silicone resin typically contains less than 2% silicon-bonded hydroxyl groups and can be prepared by: the product described by Daudt et al is reacted with an end-capping agent containing unsaturated organic groups and an end-capping agent that does not contain aliphatic unsaturated groups in an amount sufficient to provide from 3 to 30 mole percent of the unsaturated organic groups in the final product. Examples of blocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable capping agents are known in the art and are exemplified in U.S. Pat. nos. 4,584,355, 4,591,622; and 4,585,836. A single blocking agent or a mixture of such agents may be used to prepare the siloxane resin used as starting material i).

Raw material ii)

The polydiorganosiloxane used to prepare starting material B) comprises units of the formula: (R)^2' ₃SiO_1/2)iiAnd (R)₂SiO_2/2)_hh(D unit) wherein R and R^2’As mentioned above, the subscript hh is 20 to 1000 and subscript ii has an average value of 2.

Alternatively, the starting material ii) may comprise a polydiorganosiloxane of the formula:

formula (I'): r₂R²SiO(R₂SiO)_a(RR²SiO)_bSiR₂R²，

Formula (I' I): r₃SiO(R₂SiO)_c(RR²SiO)_dSiR₃，

Or a combination of both (I ') and (II');

wherein R is as described above, and each R²Independently for R as above^2’The monovalent hydrocarbon group having a terminal aliphatic unsaturated group. Subscript a may be 0 or a positive number. Alternatively, subscript a has an average value of at least 2. Alternatively, subscript a may have a value ranging from 2 to 2000. Subscript b may be 0 or a positive number. Alternatively, subscript b may have an average value ranging from 0 to 2000. Subscript c may be 0 or a positive number. Alternatively, subscript c may have an average value ranging from 0 to 2000. Subscript d has an average value of at least 2. Alternatively, subscript d may have an average value ranging from 2 to 2000. Alternatively, each R is a monovalent hydrocarbon group, exemplified by alkyl groups such as methyl and aryl groups such as phenyl. Alternatively, R²Are exemplified by alkenyl groups such as vinyl, allyl, butenyl, and hexenyl; and alkynyl groups such as ethynyl and propynyl.

The starting materials ii) may comprise polydiorganosiloxanes, such as

i) A dimethylvinylsiloxy terminated polydimethylsiloxane,

ii) a dimethylvinylsiloxy terminated poly (dimethylsiloxane/methylvinylsiloxane),

iii) dimethylvinylsiloxy terminated polymethylvinylsiloxane,

iv) trimethylsiloxy-terminated poly (dimethylsiloxane/methylvinylsiloxane),

v) trimethylsiloxy-terminated polymethylvinylsiloxane,

vi) dimethylvinylsiloxy terminated poly (dimethylsiloxane/methylvinylsiloxane),

vii) dimethylvinylsiloxy terminated poly (dimethylsiloxane/methylphenylsiloxane),

viii) dimethylvinylsiloxy terminated poly (dimethylsiloxane/diphenylsiloxane),

ix) phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxanes,

x) dimethylhexenylsiloxy terminated polydimethylsiloxane,

xi) Dimethylhexenylsiloxy-terminated poly (dimethylsiloxane/methylhexenylsiloxane),

xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane,

xiii) trimethylsiloxy-terminated poly (dimethylsiloxane/methylhexenylsiloxane),

xiv) trimethylsiloxy-terminated polymethylhexenylsiloxane

xv) Dimethylhexenylsiloxy-terminated poly (dimethylsiloxane/methylhexenylsiloxane),

xvi) dimethylvinylsiloxy terminated poly (dimethylsiloxane/methylhexenylsiloxane), or

xvii) i), ii), iii), iv), v), vi), vii), viii), ix), x), xi), xiii), xiv), xv), and xvi).

Methods for preparing polydiorganosiloxanes suitable for use as starting material ii) for preparing starting material B), such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes, are well known in the art.

Starting material iii)

The starting material iii) is an alkoxy-functional organohydrogensiloxane oligomer. The starting material iii) can be prepared by a process comprising the steps of:

1) reacting a feedstock comprising:

(a) a polyorganohydrogensiloxane oligomer of the following unit formula (I):

(HR₂SiO_1/2)_e(R₃SiO_1/2)_f(HRSiO_2/2)_g(R₂SiO_2/2)_h(RSiO_3/2)_i(HSiO_3/2)_jj(SiO_4/2)_kkwherein R is as described above, and subscripts e, f, g, h, i, jj, and kk have values such that 5. gtoreq.e.gtoreq.0, 5. gtoreq.f.gtoreq.0, 10. gtoreq.0, 5. gtoreq.h.gtoreq.0, subscript i is 0 or 1, 5. gtoreq.jj.gtoreq.0, and subscript kk is 0 or 1, provided that the amount (e + g + jj) is equal to or greater than 2, and the amount (e + f + g + h + i + jj + kk) is equal to or less than 50;

(b) an aliphatically unsaturated alkoxysilane of the formula (II):

R²(R_c)Si(OR³)_(3-c)wherein R and R²As described above, each R3 is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms and subscript c is 0 or 1; and

(c) a selective hydrosilylation catalyst; and

optionally 2) isolating the alkoxy-functional organohydrogensiloxane oligomer prepared in step 1).

Component (a) useful in the process for preparing III) the above alkoxy-functional organohydrogensiloxane oligomers is a polyorganohydrogensiloxane oligomer of unit formula (III):

(HR₂SiO_1/2)_e(R₃SiO_1/2)_f(HRSiO_2/2)_g(R₂SiO_2/2)_h(RSiO_3/2)_i(HSiO_3/2)_jj(SiO_4/2)_kkwherein R is as described above, subscripts e, f, g, h, i, jj, and kk have values such that 5. gtoreq.e.gtoreq.0, 5. gtoreq.f.gtoreq.0, 10. gtoreq.0, 5. gtoreq.h.gtoreq.0, subscript i is 0 or 1, 5. gtoreq.jj.gtoreq.0, and subscript kk is 0 or 1, provided that the amount (e + g + jj) is not less than 2, and the amount (e + f + g + h + i + jj + kk) is not more than 50.

In an alternative embodiment, ingredient (a) is α, γ -hydrogen terminated organohydrogensiloxane oligomer of formula (IV):

wherein each R is independently an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 10 carbon atoms, a haloalkyl group of 1 to 6 carbon atoms, or a haloaryl group of 6 to 10 carbon atoms; and subscript a is an integer up to 20. Alternatively, subscript a is 0 to 20, or subscript a is 0 to 10; or subscript a is 0 to 5; or subscript a is 0 or 1. Alternatively, subscript a may be 2 to 10; or subscript a ranges from 2 to 5. Examples of suitable organohydrogensiloxane oligomers include 1, 1, 3, 3,5, 5-hexamethyltrisiloxane, 1, 3, 3-tetramethyldisiloxane, 1, 3, 3,5, 5-hexaethyltrisiloxane, and 1, 1, 3, 3-tetraethyldisiloxane. Alternatively, ingredient (a) may be 1, 1, 3, 3-tetramethyldisiloxane.

When organohydrogensiloxane oligomers of formula (IV) are used in the process, the product comprises the resulting alkoxy-functional organohydrogensiloxane oligomer of formula (V):

wherein R and subscripts a and c are as described above, D is a divalent hydrocarbon group having 2 to 18 carbon atoms, with the proviso that > 90 mole% of D is a linear divalent hydrocarbon group.

In an alternative embodiment, the organohydrogensiloxane oligomer of ingredient (a) has the unit formula (VI): (HR)₂SiO_1/2)₃(R₂SiO_2/2)_q(RSiO_3/2) Wherein the subscript q is 0 to 3. The polyorganohydrogensiloxane oligomer of the unit formula can have the formula (VII):

wherein R is as described above. Examples of such organohydrogensiloxane oligomers include those of the formula (Me)₂HSiO_1/2)₃(PrSiO_3/2) Of siliconAn alkylene oxide, wherein Me represents a methyl group and Pr represents a propyl group.

When the organohydrogensiloxane oligomer used for component (a) in the above method has unit formula (VI), the product comprises an alkoxy functional organohydrogensiloxane oligomer of formula (VIII), wherein formula (VIII) is:

wherein R and subscript c are as described above, each D is independently a divalent hydrocarbon group having 2 to 18 carbon atoms, with the proviso that > 90 mole% of D are linear divalent hydrocarbon groups.

In an alternative embodiment of the present invention, the organohydrogensiloxane oligomer of ingredient (a) may have the unit formula (IX): (HR)₂SiO_1/2)₂(R₂SiO_2/2)_q(HRSiO_2/2)_rWherein R is as described above, subscript q is 0 to 3, and subscript R is 0 to 3. In this embodiment, the organohydrogensiloxane oligomer can have the formula (X):

wherein R is as described above. Examples of such organohydrogensiloxane oligomers include 1, 1, 3,5, 5-pentamethyltrisiloxane. In this embodiment, the product comprises an alkoxy-functional organohydrogensiloxane oligomer of formula (XI), formula (XII), or a combination thereof, wherein formula (XI) is

And formula (XII) is

Wherein R and subscript c are as described above.

In an alternative embodiment, the component a) is an organohydrogensiloxaneThe oligomers are cyclic. The cyclic organohydrogensiloxane oligomer may have the unit formula: (R)₂SiO_2/2)_v(RHSiO_2/2)_sWherein R is as described above, subscript s.gtoreq.3, and subscript v.gtoreq.0. Alternatively, subscript s may be 3 to 14; or 3 to 9, or 3 to 6, or 3 to 5, or 4. Alternatively, subscript v may be 0 to 14; or 0 to 9, or 0 to 6, or 0 to 5, or 0. When the cyclic organohydrogensiloxane oligomer is used as ingredient (a), then the product may comprise an alkoxy-functional organohydrogensiloxane oligomer of the unit formula:

r, R therein³D, and subscripts c and v are as described above, subscript t is 0 or greater, subscript u is 1 or greater, and the amount (t + u) ═ s.

Component (b) useful in the above process is an aliphatically unsaturated alkoxysilane of the formula (II): r²(R_c)Si(OR³)_(3-c)Wherein R, R²And R³And subscript c is as described above. Alternatively, each R³Can be a monovalent hydrocarbon group of 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, each R3 can be methyl.

Ingredient (b) may comprise an aliphatically unsaturated alkoxysilane, exemplified by dialkoxysilanes such as dialkenyldialkoxysilanes; trialkoxysilanes, such as alkenyltrialkoxysilanes; or a combination thereof. Examples of suitable aliphatically unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, vinyltriethoxysilane, hexenyltrimethoxysilane, vinylmethyldimethoxysilane, hexenylmethyldimethoxysilane, hexenyltriethoxysilane, and combinations thereof, or vinyltrimethoxysilane.

Component (a) and component (b) are present in relative molar amounts of component (a) to component (b) in a ratio of from 1: 1 to > 1: 1, or greater than or equal to 1, i.e. a ratio of (a) to (b) of > 1: 1. Alternatively, the ratio of (a) to (b) may be in the range of 5: 1 to 1: 1, alternatively 2: 1 to 1: 1, alternatively 1.5: 1 to 1: 1. Without being bound by theory, it is believed that a molar excess of component (a) relative to component (b) may favorably affect the yield of the product.

Component (c) which can be used in the process for preparing the starting material iii) is a selective hydrosilylation catalyst. In one embodiment, ingredient (c) is a cobalt complex. The cobalt complex has the formula: [ Co (R)⁵)_x(R⁶)_y(R⁷)_w]_zWherein the amount (w + x + y) ═ 4, and the subscript z is 1 to 6. Each R⁵Is selected from carbon monoxide (CO) and isocyanide (CNR)⁸) Cyanoalkyl (NCR)⁸)，NO⁺(referred to as nitrosyl or nitrosonium ion) or Cyano (CN)^-) Wherein each R is⁸Independently an alkyl group having 1 to 18 carbon atoms. For R⁵The positively charged nitrosyl ligand of (a) positively charges the catalyst. When R5 is positively charged, there will be a negatively charged counter anion such as a halogen atom (e.g., Cl or Br), tetrafluoroborate, hexafluorophosphate or triflate. The negatively charged cyano ligand negatively charges the catalyst. When R is⁵When negatively charged, there are positively charged counter cations such as sodium, potassium, tetrabutylammonium or bis (triphenylphosporanium).

Each R⁶Independently, a phosphine ligand, exemplified by a diphenylphosphinoalkane ligand, such as diphenylphosphinoethane (dppe) or diphenylphosphinomethane (dppm). When subscript y > 0, then subscript z may be at least 2.

Each R⁷As ligands, e.g. anionic ligands such as halides (e.g. Br)^-Or Cl^-) Alkoxides OR related oxygen-containing compounds (OR)^8-Or acetyl pyruvate), amides (NR)⁸ ₂ ^-) Alkyl radicals of 1 to 18 carbon atoms, or hydrides (H)^-). In some cases, it is desirable to activate the complex to remove the ligand. By using hydrides such as Li [ HBEt ]₃]Treatment, or reduction with silver salts or alkali metals, e.g. sodium or lithium, to activate halidesWherein Et represents an ethyl group. The alkoxide or amide may be activated upon reaction with a hydrosilane (with the hydrosilane alone or in a catalytic reaction). For alkyl ligands (anionic carbon ligands, such as [ CH)₂SiMe₃]^-Wherein Me represents a methyl group, or Me^-Or butyl^-) These may also be activated when hydrosilanes are used.

The hydride ligand is typically present in the active form of the catalyst. When Co is present₂(CO)₈When used as a catalyst, in situ activation to form Co (H) (CO) is desirable₄。

When a cobalt complex is used, the process for preparing the starting material iii) described herein can be carried out at atmospheric pressure of 1 atmosphere or more. Alternatively, the process may be carried out at 1 atmosphere to 1.5 atmospheres. Step 1) may be carried out at 0 ℃ to 150 ℃, or 20 ℃ to 150 ℃, or 30 ℃ to 150 ℃, or 50 ℃ to 100 ℃. The temperature used for heating in step 1) depends on various factors, including the pressure selected, however, heating may be carried out at least 20 ℃ to ensure that the reaction proceeds sufficiently rapidly to be practical. The upper limit of the temperature during heating is not critical and depends on the selected composition, i.e. the upper limit should be such that the composition does not evaporate out of the reactor selected for carrying out the process. Alternatively, the heating may be 250 ℃ to 150 ℃, or 30 ℃ to 100 ℃. The exact temperature selected will depend on various factors including the choice of ligand present on the catalyst. For example, when Co is used₂(CO)₈When desired, the reaction temperature may be lower, such as from 0 ℃ to 50 ℃. This may impart improved storage stability to the catalyst and allow higher reaction temperatures when the catalyst comprises dppm or dppe ligands. For example, when the catalyst is Co₂(CO)₆(dppm), which can be stored at room temperature, and Co₂(CO)₈Can be decomposed unless stored at low temperatures (typically < 0 ℃).

Alternatively, ingredient (c) may be an iridium complex of the formula: [ Ir (R)⁹)_xx(R¹⁰)_yy]_zzWherein the subscript xx is 1 or 2, R⁹Is a1, 5-cyclooctadiene ligand or 2,5-norbornadiene ligands with subscript yy of 0 to 2, alternatively 0 or 1, R¹⁰Is an activatable ligand and subscript zz is 1 or 2. Alternatively, subscript zz ═ 2. With respect to R¹⁰The activation of (a) may be carried out by any convenient method, such as heating at a temperature less than the boiling point of the organohydrogensiloxane oligomer, addition of a silver salt, or by a photochemical or electrochemical method in step 1) of the method described herein. Is suitable for R¹⁰Examples of suitable halogen atoms include bromine (Br), chlorine (Cl), and iodine (I). alternatively, the halogen atom may be Cl. β ketoester ligands include acetylacetone (acac). examples of halogenated β ketoesters include hexafluoroacetylacetone (hfac). examples of alkoxy ligands include methoxy, ethoxy, and propoxy₃CN, acetonitrile and Tetrahydrofuran (THF). Examples of suitable aryl ligands include phenyl, benzyl, or indenyl. Examples of suitable heteroaryl ligands include pyridine.

Exemplary iridium catalysts suitable for component (c) include, but are not limited to, [ Ir (I) CODCl-dimer, Ir (I) CODacac, Ir (I) COD₂BARF, Ir (I) COD (OMe) -dimer, Ir (I) COD (hfacac), Ir (I) COD (CH)₃CN)₂Ir (I) COD (pyridine), Ir (I) COD (indene, base) and mixtures thereof; wherein COD represents a1, 5-cyclooctadiene group, BARF represents tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, acac represents acetylacetone, and hfacac represents hexafluoroacetylacetone.

When an iridium complex is used, step 1) of the process for preparing the starting material iii) may be carried out in an oxidizing agent such as oxygen (O)₂) Organic oxidizers such as quinones, or inorganic oxidizers such as oxides (as described, for example, in DE 102005030581). Alternatively, the stabilizer may be a diene or polyalkene added in excess to further stabilize the Ir catalyst to allow better overall performance (as described, for example, in WO 2008107332 a1, EP 1156052B 1, EP 1633761B 1, EP 1201671B 1, DE 10232663C 1).

The process may be carried out at atmospheric pressure of 1 atmosphere or higher. Alternatively, the process may be carried out at 1 atmosphere to 1.5 atmospheres. Step 1) may be carried out at 0 ℃ to 150 ℃, or 50 ℃ to 150 ℃, or 60 ℃ to 150 ℃, or 50 ℃ to 100 ℃. The temperature used for heating in step 1) depends on various factors, including the pressure selected, however, heating may be carried out at least 70 ℃ to ensure that the reaction proceeds sufficiently rapidly to be practical. The upper limit of the temperature during heating is not critical and depends on the selected composition, i.e. the upper limit should be such that the composition does not evaporate out of the reactor selected for carrying out the process. Alternatively, the heating may be from 70 ℃ to 150 ℃, or from 70 ℃ to 100 ℃.

Alternatively, ingredient (c) may be a chelated diphosphine rhodium complex. The chelated diphosphine rhodium complex can have the formula (c 1): [ R ]⁴(R¹¹ ₂P)₂RhR¹²]₂Formula (c 2): [ R ]⁴(R¹¹ ₂P)₂Rh(R¹⁴)]R¹³Or mixtures thereof. In each of the formula (c1) and the formula (c2), each R⁴Independently a divalent hydrocarbon group, each R¹¹Independently a monovalent hydrocarbon group, and each R¹²Independently a negatively charged ligand, and each R¹³Independently, an anion. For R⁴The divalent hydrocarbon group of (a) may be an alkylene group of 1 to 6 carbon atoms. Alternatively, R⁴May be methylene, ethylene or hexylene; or R4 may be ethylene.

For R¹¹The monovalent hydrocarbon group of (a) may be an alkyl group or an aryl group, as described below. Alternatively, for R¹¹The alkyl group of (a) may be methyl, ethyl or propyl. Is suitable for R¹¹Examples of aryl groups of (a) are, but not limited to, phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl. Alternatively, R¹¹May be an ethyl group or a phenyl group.

Is suitable for R¹²Examples of the negatively charged ligand of (a) include halogen atoms, alkoxy ligands, aryl ligands, and heteroaryl ligands. Exemplary packages of suitable halogen atomsIncluding bromine (Br), chlorine (Cl) and iodine (I). Alternatively, the halogen atom may be Cl. Examples of alkoxy ligands include methoxy, ethoxy, and propoxy. Alternatively, the alkoxy ligand may be methoxy. Examples of suitable aryl ligands include phenyl, benzyl, or indenyl.

R¹³Is an anion. Alternatively, the anion may be referred to by those skilled in the art as a "weakly coordinating anion" or a "noncoordinating anion" and includes perchlorate, triflate, tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, methyltris (pentafluorophenyl) borate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, hexafluoroantimonate, hexafluorophosphate, [ Al (C (CF) s₃)₃)₄]Carboranes such as [ HCB ]₁₁Me₅Br₆]- (wherein Me represents methyl).

In the formula (c2), R¹⁴Represents a donor ligand. Suitable donor ligands are nitriles such as acetonitrile, cyclized or non-cyclized ethers such as tetrahydrofuran or diethyl ether, dimethyl sulfoxide, alkenes such as 1, 2-cis-cyclooctene or 1-octene or ethylene, dienes such as 1, 5-cyclooctadiene or 2, 5-norbornadiene or 1, 5-hexadiene, ketones such as ethanones, or alkynes such as acetylene or 1, 2-tolane.

Exemplary rhodium catalysts suitable for ingredient (c) include, but are not limited to, [1, 2-bis (diphenylphosphino) ethane ] dichlorodirhodium and [1, 2-bis (diethylphosphino) ethane ] dichlorodirhodium, and mixtures thereof.

When a rhodium catalyst is used for component (c), the process for preparing the starting material iii) may be carried out under inert conditions, i.e. wherein the vessel for the component is purged with an inert gas such as nitrogen prior to the reaction. The oligomers used can be prepared by reaction with basic Al₂O₃Contact to reduce the acid concentration prior to step 1). The process may be carried out at atmospheric pressure of 1 atmosphere or higher. Alternatively, the process may be carried out at 1 atmosphere to 1.5 atmospheres. Step 1) may be carried out at 0 ℃ to 150 ℃, or 50 ℃ to 150 ℃, or 60 ℃ to 150 ℃, or 50 ℃ to 100 ℃. The temperature used for heating in step 1) depends on various factors, including the choiceHowever, the heating may be carried out at a temperature of at least 70 ℃ to ensure that the reaction proceeds sufficiently rapidly to be practical. The upper limit of the temperature during heating is not critical and depends on the selected composition, i.e. the upper limit should be such that the composition does not evaporate out of the reactor selected for carrying out the process. Alternatively, the heating may be from 70 ℃ to 150 ℃, or from 70 ℃ to 100 ℃.

The amount of ingredient (c) used in step 1) of the above process depends on a number of factors, including the particular polyorganohydrogensiloxane oligomer selected for ingredient (a), the particular aliphatically unsaturated alkoxysilane selected for ingredient (b), and the temperature to which the mixture can be heated without allowing the polyorganohydrogensiloxane oligomer selected for ingredient (a) to boil dry. However, the amount of component (c) may be sufficient to provide a molar amount of cobalt metal in the mixture of from one part per million (ppm) to 100ppm, alternatively from 5ppm to 80ppm, alternatively from 5ppm to 20ppm, based on the combined weight of components (a) and (b). Without being bound by theory, it is believed that when the catalyst is loaded to the upper end of the range, the yield may decrease due to gel formation as a by-product, but selectivity to the compound of formula (IV) is still favored. The process may also optionally include deactivating or removing the catalyst. However, at appropriate catalyst loadings, the step of deactivating or removing the catalyst may be omitted.

Step 1) of the above process produces a product comprising an alkoxy-functional organohydrogensiloxane oligomer. The alkoxy-functional organohydrogensiloxane oligomer has the unit formula (X):

wherein

R、R³And subscripts c, f, h, i, and kk are as described above, subscript b is 0 to 2, m > 0, and the amount (m + n + o + p) ═ e + g + jj), and each D is independently a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that > 90 mole% of all D groups produced in step 1) are linear. The methods described herein provide benefits compared toThe alkoxy-functional organohydrogensiloxane oligomers are produced with high selectivity to the β -adduct compound (i.e., where D is linear) and with no or lower amounts of the corresponding α -adduct compound using existing methods of other catalysts.

The ingredients in step 1) of the above process form a homogeneous or heterogeneous mixture. For example, one or more additional ingredients, in addition to the above ingredients (a), (b), and (c), may optionally be used in the methods and compositions described herein. When present, the additional component may be (d) a solvent or (e) a stabilizer, or both (d) and (e).

Ingredient (d) is a solvent that can be added to the mixture used in step 1) of the process described herein. One or more of ingredients (a), (b) and/or (c) may be provided in a solvent. For example, component (c) may be dissolved in a solvent that has been added to the mixture of step 1). The solvent may facilitate contact of the reactants with the catalyst, flow of the mixture, and/or introduction of specific components such as the catalyst. Solvents for use herein are those that aid in the fluidization of the mixture ingredients but do not substantially react with either of these ingredients. The choice of solvent may be based on the solubility and volatility of the ingredients in the mixture. Solubility refers to a solvent sufficient to dissolve the components of the mixture. Volatility refers to the vapor pressure of a solvent. If the solvent is too volatile (has too high a vapor pressure), the solvent cannot remain in solution during heating. However, if the solvent is not sufficiently volatile (low vapor pressure), the solvent may be difficult to remove from the product or separate from the alkoxy-functional organohydrogensiloxane oligomer.

The solvent may be an organic solvent. The organic solvent may be an aromatic hydrocarbon such as benzene, toluene, or xylene, or a combination thereof. Ingredient (d) may be a solvent. Alternatively, ingredient (d) may comprise two or more different solvents.

The amount of solvent may depend on a variety of factors, including the particular solvent selected and the amounts and types of other ingredients selected for the mixture. However, the amount of solvent may range from 0% to 99%, or 1% to 99%, or 2% to 50% when present, based on the weight of the mixture.

The process may also optionally include one or more additional steps, the process may also include the step of recovering from the product a fraction comprising alkoxy-functional organohydrogensiloxane oligomers because alkoxy-functional organohydrogensiloxane oligomers may include β -adduct compounds (i.e., where D is linear) and the corresponding α -adduct compounds (i.e., where D is non-linear) that are difficult and/or expensive to separate from each other, a fraction comprising both β -adduct compounds and α -adduct compounds may be recovered from the product after step 1) above, it is desirable that the fraction comprises > 90% of β adduct mixture, or > 90% to 100% of β adduct mixture, or 92% to 100%, or > 90% to < 100%, or 92% to < 100%, or 95% to < 100% of β adduct mixture, based on the combined amount of β adduct compounds and α adduct compounds in the fraction.

For example, a hydrosilylation reaction of SiH groups in an alkoxy-functional organohydrogensiloxane oligomer of formula (X) with an aliphatic unsaturated group bonded to silicon feedstock i) and feedstock ii) will produce an alkoxy-functional polyorganosiloxane resin polymer blend.

Raw material iv)

The feed iv) is a hydrosilylation catalyst different from the catalyst used to prepare the feed iii). Conventional catalysts suitable for catalyzing hydrosilylation reactions are known in the art and are commercially available. Such hydrosilylation catalysts can be platinum group metals, such as platinum. Alternatively, the hydrosilylation catalyst may be a compound of such a metal, for example chloroplatinic acid, chloroplatinic acid hexahydrate, platinum dichloride, and complexes of the compound with low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core/shell type structure. Complexes of platinum with low molecular weight organopolysiloxanes include complexes of 1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane with platinum. These complexes may be microencapsulated in a resin matrix. Exemplary hydrosilylation catalysts are described in U.S. Pat. nos. 3,159,601; 3,220,972; 3,296,291, respectively; 3,419,593; 3,516,946, respectively; 3,814, 730; 3,989,668, respectively; 4,784,879, respectively; 5,036,117, respectively; and 5,175,325 and EP 0347895B. Microencapsulated hydrosilylation catalysts and methods for making them are known in the art, as exemplified in U.S. Pat. Nos. 4,766,176 and 5,017,654. The combination of the starting materials may be carried out at elevated temperatures, such as by heating at 50 ℃ to 250 ℃.

Raw material C)

The raw material C) in the adhesive composition is a condensation reaction catalyst. The condensation reaction catalyst may be selected from the common condensation catalysts effective for silanol-silanol condensation reactions, including organometallic compounds, amines, and a wide range of organic and inorganic bases and acids. The organometallic compounds include organic compounds of tin, titanium, zinc, zirconium, hafnium, etc. The condensation reaction catalyst can be organic tin compound and organic titanium compound. Exemplary organotin compounds may be selected from: a) n-tin salts of carboxylic acids, such as: i) dibutyltin dilaurate, ii) dimethyltin dilaurate, iii) di (n-butyl) tin diketonate, iv) dibutyltin diacetate, v) dibutyltin maleate, vi) dibutyltin diacetylacetonate, vii) dibutyltin dimethoxide, viii) methoxycarbonylphenyltin trisuberate, ix) dibutyltin dioctoate, x) dibutyltin diformate, xi) isobutyltin triscalate, xii) dimethyltin dibutyrate, xiii) dimethyltin dineodecanoate, xiv) dibutyltin dineodecanoate, xv) triethyltin tartrate, xvi) dibutyltin dibenzoate, xvii) butyltin tris-2-ethylhexanoate, xviii) dioctyltin diacetate, xix) tin octoate, xx) tin oleate, xxi) tin butyrate, xxii) tin naphthenate, xxiii) dimethyltin dichloride; b) tin (II) salts of organic carboxylic acids, such as: xxiv) tin (II) diacetate, xxv) tin (II) dioctoate, xxvi) tin (II) diethylhexanoate, xxvii) tin (II) dilaurate; c) stannous salts of carboxylic acids, such as: xxviii) stannous octoate, xxix) stannous oleate, xxx) stannous acetate, xxxi) stannous laurate, xxxii) stannous stearate, xxxiii) stannous naphthenate, xxxiv) stannous hexanoate, xxxv) stannous succinate, xxxvi) stannous octoate, and combinations of two or more of i) to xxxvi), exemplary organic titanium compounds may be selected from: i) tetra-n-butyl titanate, ii) tetraisopropyl titanate, iii) tetra-tert-butyl titanate, iv) tetra (2-ethylhexyl) titanate, v) acetylacetonatotitanate chelate, vi) ethylacetoacetate titanate chelate, vii) triethanolamine titanate chelate, and combinations of two or more of i), ii), iii), iv), v), vi), and vii).

The amount of condensation reaction catalyst in the adhesive composition depends on a variety of factors, including the selection of other raw materials, whether any additional raw materials are added, and the end use of the adhesive composition. However, the condensation reaction catalyst may be present in an amount in the range of 0.01% to 25% based on the combined weight of all raw materials in the adhesive composition. Alternatively, the condensation reaction catalyst may be present in an amount of from 0.1% to 25%, alternatively from 0.1% to 15%, alternatively from 0.5% to 10%, alternatively from 0.1% to 5%.

Raw material D)

The raw material D) in the adhesive composition is a radical initiator. The radical initiator may comprise an azo compound or an organic peroxide compound. Suitable azo compounds include azobenzene, azobenzene-p-sulfonic acid, azobisdimethylvaleronitrile, azobisisobutyronitrile, and combinations thereof. Suitable organic peroxide compounds include dialkyl peroxides, diaryl peroxides, diacyl peroxides, alkyl hydroperoxides and aryl hydroperoxides. Examples of specific organic peroxide compounds are benzoyl peroxide; dibenzoyl peroxide; 4-monochlorobenzoyl peroxide; dicumyl peroxide; tert-butyl peroxybenzoic acid; tert-butyl cumyl peroxide; tert-butyloxy 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane; 2, 4-dichlorobenzoyl peroxide; di-tert-butyl peroxydiisopropylbenzene; 1, 1-bis (tert-butylperoxy) -3, 3, 5-trimethylcyclohexane; 2, 5-di-tert-butylperoxyhexane-3, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; tert-butyl cumyl peroxide; or a combination of two or more thereof.

The amount of free radical initiator added to the adhesive composition depends on a variety of factors including the type and amount of condensation reaction catalyst selected and the selection of other raw materials in the adhesive composition, however, the free radical initiator may be present in an amount of 0.1% to 5%, alternatively 0.2% to 3%, alternatively 0.5% to 2%, based on the combined weight of all raw materials in the adhesive composition.

Additional raw materials

The above-mentioned adhesive composition may further comprise one or more additional raw materials (different from the above-mentioned raw materials a, B), C) and D) and added in addition to the above-mentioned raw materials a, B), C) and D)). The additional raw materials are selected from: E) dual cure compounds, F) adhesion promoters, G) resists, H) rheology modifiers, I) drying agents, J) crosslinkers, K) fillers, L) spacers, M) acid scavengers, N) silanol-functional polydiorganosiloxanes, O) fluorescent optical brighteners, P) chain transfer agents, Q) (meth) acrylate monomers, R) polyalkoxy-terminated polydiorganosiloxanes, S) colorants, and two or more of E), F), G), H), I), J), K), L), M), N), O), P), Q), R), and S).

Raw material E)

The above adhesive composition may optionally further comprise a raw material E) a dual curing compound. The dual cure compound is an organosilicon compound having at least one hydrolyzable group and at least one free radical reactive group per molecule. The organosilicon compounds used for the starting materials E) may comprise the formula R¹ _mmR_nnSiX_(4-mm-nn)Wherein R and R¹As mentioned above, X is a hydrolysable group, subscript mm is 1 to 2, subscript nn is 0 to 2, and the amount (mm + nn) is 2 to 3.

Each X independently represents a hydrolysable group which may be selected from: acetamido groups, acyloxy groups (such as acetoxy), alkoxy groups, amide groups, amino groups, aminoxy groups, oxime groups, ketoximino groups, and methylacetamido groups. X is not a hydroxyl group. Alternatively, each X may be an acetoxy group or an alkoxy group. Alternatively, each X is an alkoxy group such as methoxy, ethoxy, propoxy or butoxy; alternatively, it is methoxy.

Alternatively, the organosilicon compound used for starting material E) may comprise a polyorganosiloxane having the following unit formula:

(X_mmR_(3-mm)SiO_1/2)_oo(R¹R₂SiO_1/2)_pp(R₂SiO_2/2)_qq(RXSiO_2/2)_rr(R¹RSiO_2/2)_ss(R¹SiO_3/2)_ww(RSiO_3/2)_tt(SiO_4/2)_uuwherein R, R¹And X and subscript mm are as described above, subscript oo is greater than or equal to 0, subscript pp is greater than or equal to 0, subscript qq is greater than or equal to 0, subscript rr is greater than or equal to 0, subscript ss is greater than or equal to 0, subscript ww is greater than or equal to 0, and subscript uu is greater than or equal to 0, provided that the amount (oo + rr) is greater than or equal to 1, the amount (pp + ss + ww) is greater than or equal to 1, and the amount (oo + pp + qq + rr + ss + ww + tt + uu) > 2. Alternatively, subscript oo is 0 to 100, or 0 to 50, or 0 to 20, or 0 to 10, or 1 to 50, or 1 to 20, or 1 to 10. Alternatively, the subscript pp may be 0 to 100, alternatively 0 to 50, alternatively 0 to 20, alternatively 0 to 10, alternatively 1 to 50, alternatively 1 to 20, alternatively 1 to 10. Alternatively, subscript qq is 0 to 1,000, alternatively 0 to 500, alternatively 0 to 200, alternatively 0 to 100, alternatively 1 to 500, alternatively 1 to 200, alternatively 1 to 100. Alternatively, subscript rr is 0 to 100, alternatively 0 to 50, alternatively 0 to 20; or 0 to 10, or 1 to 50, or 1 to 20, or 1 to 10. Alternatively, subscript ss is 0 to 100, alternatively 0 to 50, alternatively 0 to 20, alternatively 0 to 10, alternatively 1 to 50, alternatively 1 to 20, alternatively 1 to 10. Alternatively, subscript ww is 0 to 100, alternatively 0 to 50, alternatively 0 to 20, alternatively 0 to 10, alternatively 1 to 50, alternatively 1 to 20, alternatively 1 to 10. Alternatively, subscript tt is 0 to 1,000, alternatively 0 to 500, alternatively 0 to 200; or 0 to 100, or 1 to 500, or 1 to 200, or 1 to 100. Alternatively, subscript uu is 0 to 1,000, alternatively 0 to 500, alternatively 0 to 200, alternatively 0 to 100, alternatively 1 to 500, alternatively 1 to 200, alternatively 1 to 100.

Examples of the raw material E) include silanes such as methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, acryloxypropylmethyldimethoxysilane, acryloxypropyldimethylmethoxysilane, and methacryloxypropyldimethylmethoxysilane.

The amount of dual cure compound in the adhesive composition depends on a number of factors, including the selection of other raw materials, whether any additional raw materials are added, and the end use of the composition. However, the dual cure compound may be present in an amount ranging from 0.01% to 25% based on the combined weight of all raw materials in the adhesive composition. Alternatively, the dual cure compound may be present in an amount of 0.1% to 25%, alternatively 0.1% to 15%, alternatively 0.5% to 10%, alternatively 0.1% to 5%.

Starting material F)

The above adhesive composition may optionally further comprise F) an adhesion promoter. Suitable adhesion promoters may comprise transition metal chelates, hydrocarbyloxysilanes such as alkoxysilanes, combinations of alkoxysilanes and hydroxyl functional polyorganosiloxanes, amino functional silanes, or combinations thereof. The adhesion promoter may comprise a compound having the formula R¹⁵ _aaaR¹⁶ _bbbSi(OR¹⁷)_4-(aaa+bbb)Wherein each R is¹⁵Independently a monovalent organic group having at least 3 carbon atoms; r¹⁶Contains at least one SiC-bonded substituent having an adhesion-promoting group (such as an amino, epoxy, mercapto or acrylate group); each R¹⁷Independently a saturated hydrocarbon group such as an alkyl group having 1 to 4 carbon atoms; subscript aaa has a value ranging from 0 to 2; subscript bbb is 1 or 2; and the amount (aaa + bbb) is not more than 3. Alternatively, the adhesion promoter may comprise a partial condensate of the above silane. Alternatively, the adhesion promoter may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.

Alternatively, the adhesion promoter may comprise an unsaturated compound or an epoxy-functional compound. The adhesion promoter may compriseSaturated alkoxysilanes or epoxy-functionalized alkoxysilanes. For example, the functional alkoxysilane may have the formula R¹⁸ _cccSi(OR¹⁹)_(4-ccc)Wherein the subscript ccc is 1, 2 or 3, or the subscript ccc is 1. Each R¹⁸Independently a monovalent organic group, provided that at least one R¹⁸Is an unsaturated organic group or an epoxy functional organic group. For R¹⁸Examples of epoxy-functional organic groups of (a) are 3-glycidoxypropyl and (epoxycyclohexyl) ethyl. For R¹⁸Examples of unsaturated organic groups of (a) are 3-methacryloxypropyl, 3-acryloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecenyl. Each R¹⁹Independently a saturated hydrocarbon group of 1 to 4 carbon atoms, or 1 to 2 carbon atoms. R¹⁹Examples of (b) are methyl, ethyl, propyl and butyl.

Examples of suitable epoxy-functional alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl) ethyldimethoxysilane, (epoxycyclohexyl) ethyldiethoxysilane, (epoxycyclohexyl) ethyltrimethoxysilane, (epoxycyclohexyl) ethyltriethoxysilane, and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and combinations thereof.

Alternatively, the adhesion promoter may comprise an epoxy-functional siloxane, for example the reaction product of a hydroxyl-terminated polyorganosiloxane as described above with an epoxy-functional alkoxysilane, or a physical blend of a hydroxyl-terminated polyorganosiloxane with an epoxy-functional alkoxysilane. The adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, an adhesion promoter is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and the reaction product of a hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl/dimethylsiloxane copolymer.

Alternatively, the adhesion promoter may include an amino-functional silane, such as an amino-functional alkoxysilane, exemplified by: h₂N(CH₂)₂Si(OCH₃)₃、H₂N(CH₂)₂Si(OCH₂CH₃)₃、H₂N(CH₂)₃Si(OCH₃)₃、H₂N(CH₂)₃Si(OCH₂CH₃)₃、CH₃NH(CH₂)₃Si(OCH₃)₃、CH₃NH(CH₂)₃Si(OCH₂CH₃)₃、CH₃NH(CH₂)₅Si(OCH₃)₃、CH₃NH(CH₂)₅Si(OCH₂CH₃)₃、H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃、H₂N(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃、CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃、CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃、C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃、C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃、H₂N(CH₂)₂SiCH₃(OCH₃)₂、H₂N(CH₂)₂SiCH₃(OCH₂CH₃)₂、H₂N(CH₂)₃SiCH₃(OCH₃)₂、H₂N(CH₂)₃SiCH₃(OCH₂CH₃)₂、CH₃NH(CH₂)₃SiCH₃(OCH₃)₂、CH₃NH(CH₂)₃SiCH₃(OCH₂CH₃)₂、CH₃NH(CH₂)₅SiCH₃(OCH₃)₂、CH₃NH(CH₂)₅SiCH₃(OCH₂CH₃)₂、H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂、H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂、CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂、CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂、C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂、C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂And combinations thereof.

Alternatively, the adhesion promoter may comprise a transition metal chelate. Suitable transition metal chelates include titanates, zirconates (such as zirconium acetylacetonate), aluminum chelates (such as aluminum acetylacetonate), and combinations thereof.

Alternatively, the adhesion promoter may comprise a triazine-based compound that has the function of reacting with raw material a), raw material B), or (when present) raw material E), or two or more thereof. The triazine ring may be mono-, di-, or tri-substituted, and at least one of the substituents is a reactive functional group. The functional group may be a radical reactive functional group or a condensation reactive functional group. Examples of triazine compounds having a radical-reactive functional group include triallyl isocyanurate, diallyl propyl isocyanurate, tris (methacryloxypropyl) isocyanurate, triallyl oxytriazine, trimethacryloxytriazine, triacryloylhexahydrotriazine, and tris [2- (acryloyloxy) ethyl ] isocyanurate. Examples of the triazine compound having a condensation-reactive group include 2, 4, 6-tris (methyldimethoxysilyl) triazine, and tris [3- (trimethoxysilyl) propyl ] isocyanurate.

The exact amount of adhesion promoter will depend on a variety of factors, including the selection and amount of other materials in the adhesive composition. However, the adhesion promoter, when present, may be added to the adhesive composition in an amount of from 0.01 to 50 parts by weight, alternatively from 0.01 to 10 parts by weight, alternatively from 0.01 to 5 parts by weight, based on the combined weight of all raw materials in the adhesive composition. Examples of suitable adhesion promoters are described in U.S. patent 9,156,948.

Raw material G)

The adhesive composition may optionally further comprise a raw material G) a resist. Examples of suitable resists include benzotriazole, mercaptobenzothiazole, mercaptobenzotriazole, and commercially available resists such as the 2, 5-dimercapto-1, 3, 4-thiadiazole derivatives (r.t. vanderbilt, Norwalk, Connecticut, u.s.a.) available from van der bilt corporation of Norwalk, Connecticut, usa

826) And alkyl thiadiazoles (

484). Examples of suitable resists are those described in us patent 9,156,948. When present, the amount of resist may be 0.05% to 0.5% based on the combined weight of all raw materials in the adhesive composition.

Starting material H)

The adhesive composition may optionally further comprise up to 5%, alternatively 1% to 2%, of feedstock H) rheology modifier, based on the combined weight of all feedstocks in the composition. Rheology modifiers are commercially available. Examples of suitable rheology modifiers include polyamides, hydrogenated castor oil derivatives, metal soaps, microcrystalline waxes, and combinations thereof. Examples of suitable rheology modifiers are those described in U.S. patent No. 9,156,948. The amount of rheology modifier depends on a variety of factors, including the particular rheology modifier selected and the selection of other raw materials used in the composition. However, the amount of rheology modifier can be from 0 parts to 20 parts, alternatively from 1 part to 15 parts, alternatively from 1 part to 5 parts, based on the combined weight of all raw materials in the composition.

Raw material I)

The above composition may optionally further comprise a raw material I) desiccant. The desiccant binds water from various sources. For example, the drying agent may bind by-products of the condensation reaction, such as water and alcohol. Examples of suitable desiccants are disclosed in, for example, U.S. patent 9,156,948. Examples of suitable adsorbents for the desiccant can be inorganic particles, for example zeolites such as chabazite, mordenite and analcime; molecular sieves such as alkali metal aluminosilicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof. The adsorbent may have a particle size of 10 microns or less. The adsorbent may have an average pore size sufficient to adsorb water and alcohol, e.g.

(angstroms) or less.

Alternatively, the desiccant may chemically bind water and/or other byproducts. An amount of silane crosslinker added to the composition (in addition to any silane crosslinker used as feedstock J) may act as a chemical desiccant. Without wishing to be bound by theory, it is believed that the chemical drying agent may be added to the dry portion of the multi-part composition after the parts of the composition are mixed together to render the composition anhydrous. For example, alkoxysilanes suitable as desiccants include vinyltrimethoxysilane, vinyltriethoxysilane, isobutyltrimethoxysilane and combinations thereof. The amount of desiccant will depend on the particular desiccant selected. However, when raw material I) is a chemical desiccant, the amount may range from 0 parts to 15 parts, alternatively from 0 parts to 10 parts, alternatively from 0 parts to 5 parts, alternatively from 0.1 parts to 0.5 parts, based on the combined weight of all raw materials in the composition.

Raw material J)

The above composition may optionally further comprise raw material J) a crosslinking agent. The crosslinking agent may comprise a silane crosslinking agent having hydrolyzable groups or a partial or complete hydrolysis product thereof. The crosslinking agent has on average more than two substituents per molecule which react with the hydrolyzable groups on the starting material B). Examples of silane crosslinking agents suitable for the starting material J) can have the following general formula: r²⁰ _dddSi(R²¹)_(4-ddd)Wherein each R is²⁰Independently a monovalent hydrocarbon group such as an alkyl group; each R²¹Is a hydrolyzable substituent, which may be the same group as X described above. Alternatively, each R²¹May be, for example, a hydrogen atom, a halogen atom, an acetamido group, an acyloxy group (such as acetoxy), an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, or a methylacetamido group; and each instance of subscript ii may be 0, 1, 2, or 3. For silane crosslinkers, subscript ii has an average value of greater than 2. Alternatively, subscript ddd may have a value in the range of 3 to 4. Alternatively, each R²¹May be independently selected from hydroxyl, alkoxy, acetoxy, amido or oxime. Alternatively, the silane crosslinker may be selected from: acyloxysilanes, alkoxysilanes, ketoximosilanes, and hydroxyiminosilanes.

The silane crosslinking agent may include an alkoxysilane, which is exemplified by: dialkoxysilanes such as dialkyldialkoxysilanes; trialkoxysilanes, such as alkyltrialkoxysilanes; a tetraalkoxysilane; or a partial or complete hydrolysis product thereof, or another combination thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and combinations thereof, and alternatively methyltrimethoxysilane. Examples of suitable tetraalkoxysilanes include tetraethoxysilane. Alternatively, the silane crosslinking agent may include an acyloxysilane, such as an acetoxysilane. Acetoxysilanes include tetraacetoxysilanes, organotriacetoxysilanes, diorganodiacetoxysilanes, or combinations thereof. Exemplary acetoxysilanes include, but are not limited to, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, phenyltriacetoxysilane, octyltriacetoxysilane, dimethyldiacetoxysilane, phenylmethyldiacetoxysilane, vinylmethyldiacetoxysilane, diphenyldiacetoxysilane, tetraacetoxysilane, and combinations thereof. Alternatively, the crosslinking agent may comprise an organic triacetoxysilane, for example a mixture comprising methyl triacetoxysilane and ethyl triacetoxysilane. Examples of silanes suitable for use in feedstock J) containing both alkoxy and acetoxy groups that may be used in the composition include methyldiethoxysilane, methylacetoxydimethoxysilane, vinyldiacetoxymethoxysilane, vinylacetoxydimethoxysilane, methyldiacetoxyloxyethoxysilane, methylacetoxydiethoxysilane, and combinations thereof.

Alternatively, the crosslinking agent may comprise amino functional groups such as: h₂N(CH₂)₂Si(OCH₃)₃、H₂N(CH₂)₂Si(OCH₂CH₃)₃、H₂N(CH₂)₃Si(OCH₃)₃、H₂N(CH₂)₃Si(OCH₂CH₃)₃、CH₃NH(CH₂)₃Si(OCH₃)₃、CH₃NH(CH₂)₃Si(OCH₂CH₃)₃、CH₃NH(CH₂)₅Si(OCH₃)₃、CH₃NH(CH₂)₅Si(OCH₂CH₃)₃、H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃、H₂N(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃、CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃、CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃、C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃、C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃、H₂N(CH₂)₂SiCH₃(OCH₃)₂、H₂N(CH₂)₂SiCH₃(OCH₂CH₃)₂、H₂N(CH₂)₃SiCH₃(OCH₃)₂、H₂N(CH₂)₃SiCH₃(OCH₂CH₃)₂、CH₃NH(CH₂)₃SiCH₃(OCH₃)₂、CH₃NH(CH₂)₃SiCH₃(OCH₂CH₃)₂、CH₃NH(CH₂)₅SiCH₃(OCH₃)₂、CH₃NH(CH₂)₅SiCH₃(OCH₂CH₃)₂、H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂、H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂、CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂、CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂、C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂、C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂Or combinations thereof, and combinations thereof. Examples of suitable silane crosslinking agents are disclosed in U.S. patent No. 9,156,948.

Alternatively, the crosslinker may comprise a multifunctional (meth) acrylate crosslinker, such as exemplified by di (meth) acrylate. Examples of such cross-linking agents are: ethylene glycol dimethacrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, bis-methacryloxy carbonate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triglycidyl ether, trimethylolpropane tris (2-methyl-1-aziridine) propionate, trimethylolpropane trimethacrylate, acrylate-terminated urethanes comprising a prepolymer, polyether diacrylate, and dimethacrylate, and combinations of two or more thereof. Suitable multifunctional (meth) acrylate crosslinkers are disclosed, for example, in U.S. patent 8,304,543, column 11, lines 46 to 65.

When present, the crosslinking agent may be added in an amount ranging from 0.1% to 10% based on the combined weight of all raw materials in the adhesive composition.

Raw material K)

The above composition may optionally further comprise K) a filler. The filler may comprise reinforcing fillers, extending fillers, conductive fillers, or combinations thereof. For example, the composition may optionally further comprise ingredient (K1) a reinforcing filler, which when present may be added in an amount of 0.1% to 95%, or 1% to 60%, based on the combined weight of all raw materials in the adhesive composition. The exact amount of ingredient (K1) depends on a variety of factors, including the form of the reaction product of the composition and whether any other fillers are added. Examples of suitable reinforcing fillers include reinforcing silica fillers such as fumed silica, silica aerosols, silica xerogels, and precipitated silicas. Fumed silicas are known in the art and are commercially available; such as fumed silica sold under the trademark CAB-O-SIL by Cabot Corporation of Massachusetts, usa (u.s.a).

The composition may optionally further comprise ingredient (K2), an extending filler, in an amount in the range of from 0.1% to 95%, alternatively from 1% to 60%, alternatively from 1% to 20%, based on the combined weight of all raw materials in the adhesive composition. Examples of bulking fillers include crushed quartz, alumina, magnesia, calcium carbonate (such as precipitated calcium carbonate), zinc oxide, talc, diatomaceous earth, iron oxide, clay, mica, chalk, titanium dioxide, zirconia, sand, carbon black, graphite, or combinations thereof. Extending fillers are known in the art and are commercially available; such as abrasive silica sold under the trade name MIN-U-SIL by U.S. silica, Berkeley Springs, WV, of Berkeley preglin, west virginia. Suitable precipitated calcium carbonates include those from the Sowey company (Solvay)

SPM and from the Sorawexi mining company (SMI)

And

100. examples of suitable fillers are described in us patent 9,156,948.

Raw material L)

The above adhesive composition may optionally further comprise L) a separator. The separator may comprise organic particles, inorganic particles, or a combination thereof. The spacers may be thermally conductive, electrically conductive, or both. The spacers may have a desired particle size, for example, the particle size may be in the range of 25 micrometers (μm) to 125 μm. The spacers may comprise monodisperse beads, such as glass or polymer (e.g., polystyrene) beads. The separator may contain thermally conductive fillers such as alumina, aluminum nitride, atomized metal powders, boron nitride, copper, and silver. The amount of spacer depends on a variety of factors including particle size distribution, pressure to be applied during use of the composition prepared by mixing the parts or the cured product prepared therefrom, temperature during use, and the desired thickness of the mixed composition or cured product prepared therefrom. However, the composition may comprise the separator in an amount ranging from 0.05% to 2%, alternatively from 0.1% to 1%, based on the combined weight of all raw materials in the composition.

Raw material M)

The above composition may optionally further comprise M) an acid scavenger. Suitable acid scavengers include various inorganic and organic compounds that are basic, such as magnesium oxide, calcium oxide, and combinations thereof. The composition may comprise from 0% to 10% of an acid scavenger, based on the combined weight of all raw materials in the composition.

Raw material N)

The above compositions may optionally further comprise N) a silanol functional polydiorganosiloxane. The starting material N) may comprise a polydiorganosiloxane of the formula: formula HOR₂SiO(R₂SiO)_eee((HO)RSiO)_fffSiR₂OH, formula R₃SiO(R₂SiO)_ggg((HO)RSiO)_hhhSiR₃Or combinations thereof, wherein R is as described above. Subscript eee may be 0 or a positive number. Alternatively, subscript eee has an average value of at least 2. Alternatively, subscript eee may have a value in the range of 2 to 2000. Subscript fff may be 0 or a positive number. Alternatively, subscript fff may have an average value ranging from 0 to 2000. Subscript ggg may be 0 or a positive number. Alternatively, subscript ggg may have an average value ranging from 0 to 2000. Subscript hhh has an average value of at least 2. Alternatively, subscript hhh may have an average value ranging from 2 to 2000.

The starting materials N) may comprise polydiorganosiloxanes, such as

i) A hydroxyl-terminated Polydimethylsiloxane (PDMS),

ii) a hydroxy terminated poly (dimethylsiloxane/methylphenylsiloxane),

iii) trimethylsiloxy-terminated poly (dimethylsiloxane/methylhydroxysiloxane), and

iv) a combination of two or more of i), ii) and iii).

Hydroxyl-terminated polydiorganosiloxanes suitable for use as starting material N) may be prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes. When added to the adhesive composition, starting material N) may be present in an amount of from 0.1% to 20%, alternatively from 0.1% to 10%, alternatively from 0.1% to 5%, based on the combined weight of all starting materials in the adhesive composition.

Raw material O)

The above adhesive composition may optionally further comprise a raw material O) an optical brightener. Suitable optical brighteners are commercially available, such as 2, 5-thiophenediylbis (5-tert-butyl-1, 3-benzoxazole), commercially available as TINOPALOB. When added to the composition, the optical brightener may be present in an amount of 0.1% to 2% based on the combined weight of all raw materials in the adhesive composition.

Raw material P)

The above adhesive composition may optionally further comprise P) a chain transfer agent. When added to the adhesive composition, the chain transfer agent may be present in an amount of 0.01% to 5%, alternatively 0.01% to 2%, alternatively 0.1% to 2%, based on the combined weight of all raw materials in the composition.

Raw material Q)

The above adhesive composition may optionally further comprise a raw material Q) (meth) acrylate monomer. Examples of (meth) acrylate monomers are methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate and cyclohexylmethyl methacrylate. When added to the adhesive composition, the (meth) acrylate ester monomer may be present in an amount of from 0.1% to 35%, alternatively from 0.1% to 25%, alternatively from 0.1% to 15%, alternatively from 0.1% to 10%, based on the combined weight of all raw materials in the adhesive composition.

Raw material R)

In addition to any material which would be prepared by preparing the above-mentioned starting material B), the starting material R) is also a polyalkoxy-terminated polydiorganosiloxane. The starting material R) may be a polyalkoxy-terminated polydiorganosiloxane prepared as described above for starting material B), except that the siloxane resin is excluded. Alternatively, the starting material R) may be a polyalkoxy-terminated polydiorganosiloxane prepared via a platinum-catalyzed hydrosilylation reaction as described above.

Raw material S)

The above-mentioned binder composition may optionally further comprise a raw material S) colorant. The colorant may be a dye or a pigment, such as carbon black.

When selecting raw materials for the adhesive compositions described above, there may be overlap between the types of ingredients, as certain raw materials described herein may have more than one function. For example, certain alkoxysilanes can be used as crosslinking agents and/or adhesion promoters and/or drying agents. Certain particles may be used as fillers and spacers. When additional raw materials are added to the adhesive composition, the additional raw materials are different from each other.

Method for preparing adhesive composition

The above adhesive composition can be prepared by the following steps: 1) the raw materials B) i) organosiloxane resin and B) ii) polydiorganosiloxane are combined to form a Resin Polymer Blend (RPB). A solvent may optionally be used to homogenize the RPB. One or more of the starting materials, such as the organosiloxane resin, may be dissolved or dispersed in a solvent such as benzene, toluene, or xylene. Typically, the amount of solvent may be from 0% to 60%, alternatively from 10% to 50%, alternatively from 20% to 40%, based on the combined weight of all raw materials in the adhesive composition. The starting materials B) iii) and B) iv) as described above may be combined with RPB to form the converted RPB. The method may further comprise: 2) the converted RPB and feedstock a), C) and D) are combined by any convenient means, such as mixing. One or more additional feedstocks E) to S) as described above may be added during step 1), step 2), or both. The starting materials can be combined at from 20 ℃ to 150 ℃. The method can further comprise heating the feedstock at a temperature of 50 ℃ to 150 ℃, or 60 ℃ to 120 ℃ in step 1), step 2), or both. The pressure is not critical; the method may be performed at ambient pressure.

Examples

The following examples are intended to illustrate some embodiments of the invention and should not be construed as limiting the scope of the invention as set forth in the claims. The starting materials in table 1 were used in these examples.

Table 1: raw materials

Example 1-synthesis of a converted resin polymer blend: general protocols。

In a typical synthesis, the resin polymer blend (84.5 parts), magnesium oxide (3.57 parts), and pigment (1.02 parts) were mixed in a 2-Gal Ross mixer for 10 minutes. Methyltrimethoxysilane (0.95 parts) and hexamethyldisilazane (0.09 parts) were added to the mixture. The mixture was further blended for 10 minutes under nitrogen. Then, the temperature was raised to 60 ℃ and maintained for 30 minutes. The temperature was raised to 120 ℃ and the mixture was stripped under full vacuum (1 torr) for 60 minutes.

The mixture was cooled to 35 ℃. An end-capping agent (XCF3-6105 or linear ETM, 5.41 parts) and 1, 1, 1, 3,5, 5, 5-heptamethyltrisiloxane (4.34 parts) were added. The mixture was blended for 10 minutes under nitrogen blanket. Karstedt's catalyst (0.096 parts) was added. The reaction was then mixed again for 10 minutes. Then, the temperature was raised to 80 ℃ and maintained for 40 minutes. Once the IR indicated the hydrosilylation was complete, the mixture was stripped at 150 ℃ under full vacuum (1 torr) for 30 minutes. The product obtained is a thick liquid.

The starting materials shown in table 2 below were used to prepare the converted RPB according to the procedure in example 1.

TABLE 2

Gel time was measured at constant strain at 20 ℃ and 50% RH by an Ares G2 rheometer with parallel plates.

The catalyst was tetra-n-butyl titanate with a1 wt% loading.

Example 2 formulation of adhesive with inverted RPB

In a 10 liter Turello mixer, the dumbbell intermediate (71.73 parts), the transformed RPB (19.34 parts) provided in table 1 above, polyalkoxy-terminated PDMS (0.1 parts), and Tinopal OB (0.02 parts) were loaded. The mixture was mixed at 10 ℃ for 10 minutes. To the homogeneous mixture was added BPO (Perkadox L-50S-ps, 2.95 parts), Z-6030(1.97 parts), triallyl isocyanurate (0.49 parts) and a solution of 2-mercaptobenzothiazole (0.15 parts) in A186(0.59 parts). The mixture was mixed again at 10 ℃ for 10 minutes. A solution of tri-n-butyl titanate (0.61 part) in IBTMS (1.85 part) and a solution of APTMS (0.11 part) in IBTMS (0.11 part) were added. The preparation was mixed again at 10 ℃ for 10 minutes. The final product was degassed at 10 ℃ under vacuum of 200 torr for 30 minutes.

Adhesive compositions prepared according to the protocol in example 2 are summarized in table 3.

TABLE 3：

	Adhesive agent	Transformed RPB
Comparative, plant preparation	Comparative adhesive	Conventional capped RPB 1
			Comparative, laboratory preparation	Comparative adhesive	Transformed RPB 1
	Novel binders I	Transformed RPB 2
				Novel binders II	Transformed RPB 6

EXAMPLE 3 curing of adhesive films

Films of the adhesive were prepared by stretching a strip with a 50 mil gap (1.27mm) on an aluminum Q panel (3.5 x 10 inches). The film was cured in an oven at 100 ℃ in air for one hour. The film was allowed to cool to room temperature for 15 minutes and then its surface wetting was measured by impact testing.

Example 4 impact testing。

Impact testing was performed on a drop impact tester (Qualtech Products). A pre-weighed filter paper (Gilman, quantitative, grade 2) was placed on a cured adhesive film (thickness: 50 mils, 1.27mm) on an aluminum Q plate (3.5X 10 "). A steel block (0.3Kg) was dropped from a height of 30cm onto a cylindrical metal rod which formed a mark on the filter paper. This drop was repeated several times at different regions of the filter paper. The filter paper is carefully peeled off the sample and weighed. The difference (in milligrams) before and after impact is referred to as the surface wettability of the sample.

Example 5 curing speed of converted RPB

The cure rate test was conducted in air at 20 ℃ and 50% Relative Humidity (RH). Prior to testing, the converted RPB prepared as described above was thoroughly blended with 1 wt% tributyl titanate. The results show that the gel times of RPB treated with linear capping agents are generally much shorter than those treated with conventional capping agents. For RPB 2, an order of magnitude reduction in gel time was observed when the RPB was treated with a linear capping agent. Other characteristics of the capped RPB (including viscosity, molecular weight distribution, and alkoxy content) are substantially similar regardless of the capping agent used.

Example 6 efficacy of the converted RPB in adhesive formulations

Dumbbell intermediate 1 was selected to test the efficacy of the newly transformed RPB on surface wetting control. The commercially available EA-7100 adhesive exhibited an initial surface wet out of 24mg and dried completely in about 305 hours. The initial surface wetting of the adhesive containing the converted RPB 2 (capped with a conventional capping agent) was reduced to 16.1mg and the drying time was reduced to 170 hours. In contrast, the converted RPB 6 (capped with a linear capping agent) was able to reduce the initial surface wetting of the adhesive to 9.3mg and reduce the drying time to 60 hours.

The surface wetability data for the adhesives prepared as described in example 2 and table 3 above is summarized in table 4.

TABLE 4：

INDUSTRIAL APPLICABILITY

These examples show that the adhesive compositions described herein have faster cure times (as indicated by reduced gel times) and improved surface cure (as indicated by reduced surface wetability) under the conditions tested as described above.

Definition and usage of terms

All amounts, ratios and percentages are by weight unless otherwise indicated. The words "a", "an", and "the" each mean one or more unless otherwise indicated. The disclosure of a range includes the range itself as well as any values and endpoints contained therein. For example, disclosure of a range of 2.0 to 4.0 includes not only the range of 2.0 to 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0 individually and any other numbers contained in that range. Further, disclosure of a range such as 2.0 to 4.0 includes subsets such as 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0 and any other subset included in the range. Similarly, the disclosure of a Markush group (Markush group) includes the entire group and also includes any individual members and subgroups contained therein. For example, the disclosure of a markush group hydrogen atom, an alkyl group, an alkenyl group, or an aryl group includes the individual members alkyl; the subgroups of alkyl and aryl groups; and any other individual members and subgroups contained therein.

"alkyl" means a saturated monovalent hydrocarbon group. Examples of alkyl groups are, but are not limited to, methyl, ethyl, propyl (e.g., isopropyl and/or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl); hexyl, heptyl, octyl, nonyl, and decyl, and branched, saturated monovalent hydrocarbon groups of 6 or more carbon atoms.

"alkenyl" means a monovalent hydrocarbon group containing a double bond. Examples of alkenyl groups are, but are not limited to, ethenyl, propenyl (e.g., isopropenyl and/or n-propenyl), butenyl (e.g., isobutenyl, n-butenyl, tert-butenyl, and/or sec-butenyl), pentenyl (e.g., isopentenyl, n-pentenyl, and/or tert-pentenyl), hexenyl, heptenyl, octenyl, nonenyl, and decenyl, and such branched groups of 6 or more carbon atoms.

"alkynyl" means a monovalent hydrocarbon group containing a triple bond. Examples of alkynyl groups are, but are not limited to, ethynyl, propynyl (e.g., isopropynyl and/or n-propynyl), butynyl (e.g., isobutynyl, n-butynyl, t-butynyl, and/or s-butynyl), pentynyl (e.g., isopentynyl, n-pentynyl, and/or t-pentynyl), hexynyl, heptynyl, octynyl, nonynyl, and decynyl, and such branched groups of 6 or more carbon atoms.

"aryl" means a cyclic, fully unsaturated hydrocarbon group. Examples of aryl groups are, but not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl. Monocyclic aryl groups can have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, alternatively 5 to 6 carbon atoms. The polycyclic aryl group can have 10 to 18 carbon atoms, alternatively 10 to 14 carbon atoms, alternatively 12 to 14 carbon atoms.

"aralkyl" means an alkyl group having a pendant aryl group and/or a terminal aryl group or an aryl group having a pendant alkyl group. Exemplary aralkyl groups include tolyl, xylyl, benzyl, phenethyl, phenylpropyl, and phenylbutyl.

"carbocycle" and "carbocyclic" each mean a hydrocarbon ring. Carbocycles may be monocyclic, or alternatively may be fused, bridged or spiro polycyclic rings. Monocyclic carbocycles may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, alternatively 5 to 6 carbon atoms. Polycyclic carbocycles may have 7 to 18 carbon atoms, alternatively 7 to 14 carbon atoms, alternatively 9 to 10 carbon atoms. Carbocycles may be saturated or partially unsaturated.

"cycloalkyl" means a saturated carbocyclic ring. Examples of monocyclic cycloalkyl groups are cyclobutyl, cyclopentyl and cyclohexyl.

In general, the term "monovalent hydrocarbon group" includes alkyl, alkenyl, aryl, aralkyl, and carbocyclic groups, as defined above.

"divalent hydrocarbon group" includes alkylene groups such as ethylene, propylene (including isopropylene and n-propylene), and butylene (including n-butylene, t-butylene, and isobutylene); and pentylene, hexylene, heptylene, octylene, and branched and linear isomers thereof; arylene groups such as phenylene; and aralkylene groups such as:

alternatively, each divalent hydrocarbon group may be ethylene, propylene, butylene, or hexylene. Alternatively, each divalent hydrocarbon group may be an ethylene group or a propylene group.

"halohydrocarbon" means a hydrocarbon group as defined above, but in which one or more hydrogen atoms bonded to a carbon atom have been formally substituted by a halogen atom. For example, the monovalent halogenated hydrocarbon group may be any of an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a carbocyclic group in which one or more hydrogen atoms bonded to carbon atoms have been substituted with a halogen atom. Monovalent halogenated hydrocarbon groups include haloalkyl groups, halocarbocyclyl groups, and haloalkenyl groups. Haloalkyl groups include fluorinated alkyl groups, such as trifluoromethyl (CF)₃) Fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3, 3, 3-trifluoropropyl, 4, 4, 4-trifluorobutyl, 4, 4,3, 3-pentafluorobutyl, 5, 5, 5, 4, 4,3, 3-heptafluoropentyl, 6, 6, 6, 5, 5, 4, 4,3, 3-nonafluorohexyl and 8, 8, 8, 7, 7-pentafluorooctyl; and chlorinated alkyl groups such as chloromethyl and 3-chloropropyl. Halogenated carbocyclic groups include fluorinated cycloalkyl groups such as 2, 2-difluorocyclopropyl, 2, 3-difluorocyclobutyl, 3, 4-difluorocyclohexyl, and 3, 4-difluoro-5-methylcycloheptyl; and chlorinated cycloalkyl groups such as 2, 2-dichlorocyclopropyl, 2, 3-dichlorocyclopentyl. Haloalkenyl groups include chloroallyl groups.

Claims (15)

1. An adhesive composition comprising:

A) a poly (meth) acrylate cluster functional polyorganosiloxane comprising units of the formula:

(R₂R¹SiO_1/2)_aa(RR¹SiO_2/2)_bb(R₂SiO_2/2)_cc(RSiO_3/2)_dd(SiO_4/2)_ee((R_ff)O_{(3-ff)/ 2}SiD¹SiR_ffO_(3-ff)/2)_ggwherein each D¹Independently represent a divalent hydrocarbon group having 2 to 18 carbon atoms; each R independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 18 carbon atoms, each R¹Independently represents a methacryloyl functional alkyl group or an acryloyl functional alkyl group, subscript aa is greater than or equal to 0, subscript bb is greater than or equal to 0, amount (aa + bb) is greater than or equal to 4, subscript cc is greater than 0, subscript dd is greater than or equal to 0, subscript ee is greater than or equal to 0, subscript ff is 0, 1, or 2, and subscript gg is greater than or equal to 2;

B) a polyalkoxy terminated resin polymer blend comprising the reaction product of:

i) comprising the formula (R)^2’ ₃SiO_1/2) And (SiO)_4/2) The siloxane resin of (a), wherein each R is^2’Independently a monovalent hydrocarbon group, with the proviso that at least one R2' has a terminal aliphatic unsaturated group per molecule, wherein the silicone resin has (R^2’ ₃SiO_1/2) Unit and (SiO)_4/2) The molar ratio of the units is in the range of 0.5: 1 to 1.5: 1,

ii) comprises the formula (R)^2’ ₃SiO_1/2)_iiAnd (R)₂SiO_2/2)_hhA polydiorganosiloxane of the unit (b), wherein R is^2’Subscript hh is 20 to 1000 and subscript ii has an average value of 2, as described above;

iii) an alkoxy-functional organohydrogensiloxane oligomer, said alkoxy-functional organohydrogensiloxane oligomer having the unit formula:

(HR₂SiO_1/2)_n(R₃SiO_1/2)_f(HRSiO_2/2)_o(R₂SiO_2/2)_h(RSiO_3/2)_ii(HSiO_3/2)_p(SiO_4/2)_kk，

wherein R and D¹As mentioned above, each R³Independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, subscript b is 0 or 1, subscript c is 0, subscripts f, h, i, and kk have values such that 5 ≧ f is 0, 5 ≧ h is 0, subscript i is 0 or 1, subscript kk is 0 or 1, subscript m > 0, and an amount (m + n + f + o + h + i + p + kk) of less than or equal to 50, provided that > 90 mole% of all D groups in the capping agent are linear; and

iv) a selective hydrosilylation reaction catalyst;

C) a condensation reaction catalyst; and

D) a free radical initiator.

2. The composition of claim 1, further comprising one or more additional raw materials selected from the group consisting of: E) dual cure compounds, F) adhesion promoters, G) resists, H) rheology modifiers, I) drying agents, J) crosslinkers, K) fillers, L) spacers, M) acid scavengers, N) silanol-functional polydiorganosiloxanes, O) fluorescent optical brighteners, P) chain transfer agents, Q) (meth) acrylate monomers, R) polyalkoxy-terminated polydiorganosiloxanes, S) colorants, and two or more of E), F), G), H), I), J), K), L), M), N), O), P), Q), R), and S).

3. The adhesive composition of claim 1, wherein a) the poly (meth) acrylate cluster functional polyorganosiloxane has the formula:

wherein subscript j is 0 to 2,000,000, and each subscript k is independently 1 to 12.

4. The adhesive composition of claim 1, wherein a) the poly (meth) acrylate cluster functional polyorganosiloxane has the formula:

wherein subscript j is 0 to 2,000,000, and each subscript k is independently 1 to 12.

5. The adhesive composition of claim 1, wherein raw material B) i) has 3 to 30 mol% of vinyl groups.

6. The adhesive composition of claim 1, wherein raw material B) ii) is a polydiorganosiloxane selected from the group consisting of:

i) a dimethylvinylsiloxy terminated polydimethylsiloxane,

ii) a dimethylvinylsiloxy terminated poly (dimethylsiloxane/methylvinylsiloxane),

iii) dimethylvinylsiloxy terminated polymethylvinylsiloxane,

iv) trimethylsiloxy-terminated poly (dimethylsiloxane/methylvinylsiloxane),

v) trimethylsiloxy-terminated polymethylvinylsiloxane,

vi) dimethylvinylsiloxy terminated poly (dimethylsiloxane/methylvinylsiloxane),

vii) dimethylvinylsiloxy terminated poly (dimethylsiloxane/methylphenylsiloxane),

viii) dimethylvinylsiloxy terminated poly (dimethylsiloxane/diphenylsiloxane),

ix) phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxanes,

x) dimethylhexenylsiloxy terminated polydimethylsiloxane,

xi) Dimethylhexenylsiloxy-terminated poly (dimethylsiloxane/methylhexenylsiloxane),

xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane,

xiii) trimethylsiloxy-terminated poly (dimethylsiloxane/methylhexenylsiloxane),

xiv) trimethylsiloxy-terminated polymethylhexenylsiloxane

xv) Dimethylhexenylsiloxy-terminated poly (dimethylsiloxane/methylhexenylsiloxane),

xvi) Dimethylvinylsiloxy terminated Poly (dimethylsiloxane/methylhexenylsiloxane)

xvii) i), ii), iii), iv), v), vi), vii), viii), ix), x), xi), xiii), xiv), xv), and xvi).

7. The adhesive composition of claim 1, wherein raw material B) iii) comprises an alkoxy-functional organohydrogensiloxane oligomer of formula (V):

wherein R and subscripts a and c are as described above, D is a divalent hydrocarbon group having 2 to 18 carbon atoms, with the proviso that > 90 mole% of D is a linear divalent hydrocarbon group.

8. The adhesive composition of claim 1, wherein raw material B) iii) comprises an alkoxy-functional organohydrogensiloxane oligomer of formula (VIII), wherein formula (VIII) is:

wherein R and subscript c are as described above, each D is independently a divalent hydrocarbon group having 2 to 18 carbon atoms, with the proviso that > 90 mole% of D are linear divalent hydrocarbon groups.

9. The adhesive composition of claim 1, wherein raw material B) iii) comprises an alkoxy-functional organohydrogensiloxane oligomer of formula (XI), formula (XII), or a combination thereof, wherein formula (XI) is

And formula (XII) is

Wherein R and subscript c are as described above.

10. The adhesive composition of claim 1 wherein the raw material B) iii) comprises an alkoxy-functional organohydrogensiloxane oligomer of the unit formula:

(R₂SiO_2/2)_v(RHSiO_2/2)_t

r, R therein³D, and subscripts c and v are as described above, subscript t is 0 or greater, subscript u is 1 or greater, and the amount (t + u) ═ s.

11. The adhesive composition of claim 1, wherein the raw material B) iv) comprises a cobalt complex of the formula: [ Co (R)⁵)_x(R⁶)_y(R⁷)_w]_zWherein the amount (w + x + y) ═ 4; subscript z is 1 to 6; each R⁵Is selected from carbon monoxide (CO) and isocyanide (CNR)⁸) Cyanoalkyl (NCR)⁸)，NO⁺(referred to as nitrosyl or nitrosonium ion) or Cyano (CN)^-) Wherein each R is⁸Independently an alkyl group having 1 to 18 carbon atoms; provided that when R is⁵When positively charged, there will be a negatively charged counter anion, and when R is⁵When negatively charged, a positively charged counter cation is present; each R⁶Independently is diphenylA phosphine ligand exemplified by a bisphosphoalkane ligand, with the proviso that when subscript y > 0, then subscript z is at least 2; and each R⁷Are anionic ligands.

12. The adhesive composition according to claim 1, wherein the starting material B) iv) comprises an iridium complex of the formula: [ Ir (R)⁹)_xx(R¹⁰)_yy]_zzWherein the subscript xx is 1 or 2, R⁹Is a1, 5-cyclooctadiene ligand or a 2, 5-norbornadiene ligand, the subscript yy is 0, 1 or 2, R¹⁰Is a ligand that can activate the complex at a temperature less than the boiling point of the organohydrogensiloxane oligomer, and subscript zz is 1 or 2.

13. The adhesive composition of claim 1, wherein raw material B) iv) comprises a diphosphine rhodium chelate complex having a formula selected from the group consisting of (c1) and (c2), wherein

(c1) Is [ (R)⁴(R¹¹ ₂P)₂)RhR¹²]₂Wherein each R is⁴Independently a divalent hydrocarbon group, each R¹¹Independently a monovalent hydrocarbon group, and each R¹²Is a negatively charged ligand; and is

(c2) Is [ (R)⁴(R¹¹P)₂)Rh(R¹⁴)]R¹³Wherein R is¹³Is an anion, and R¹⁴Is a donor ligand.

14. The adhesive composition of claim 1, wherein raw material C) is selected from the group consisting of: a) n-tin salts of carboxylic acids, such as: i) dibutyltin dilaurate, ii) dimethyltin dilaurate, iii) di (n-butyl) tin diketonate, iv) dibutyltin diacetate, v) dibutyltin maleate, vi) dibutyltin diacetylacetonate, vii) dibutyltin dimethoxide, viii) methoxycarbonylphenyltin trisuberate, ix) dibutyltin dioctoate, x) dibutyltin diformate, xi) isobutyltin triscalate, xii) dimethyltin dibutyrate, xiii) dimethyltin dineodecanoate, xiv) dibutyltin dineodecanoate, xv) triethyltin tartrate, xvi) dibutyltin dibenzoate, xvii) butyltin tris-2-ethylhexanoate, xviii) dioctyltin diacetate, xix) tin octoate, xx) tin oleate, xxi) tin butyrate, xxii) tin naphthenate, xxiii) dimethyltin dichloride; b) tin (II) salts of organic carboxylic acids, such as: xxiv) tin (II) diacetate, xxv) tin (II) dioctoate, xxvi) tin (II) diethylhexanoate, xxvii) tin (II) dilaurate; c) stannous salts of carboxylic acids, such as: xxviii) stannous octoate, xxix) stannous oleate, xxx) stannous acetate, xxxi) stannous laurate, xxxii) stannous stearate, xxxiii) stannous naphthenate, xxxiv) stannous hexanoate, xxxv) stannous succinate, xxxvi) stannous octoate, and combinations of two or more of i) to xxxvi), exemplary organic titanium compounds may be selected from: i) tetra-n-butyl titanate, ii) tetraisopropyl titanate, iii) tetra-tert-butyl titanate, iv) tetra (2-ethylhexyl) titanate, v) acetylacetonatotitanate chelate, vi) ethylacetoacetate titanate chelate, vii) triethanolamine titanate chelate, and combinations of two or more of i), ii), iii), iv), v), vi), and vii).

15. The adhesive composition according to claim 1, wherein the raw material D) is selected from azo compounds or organic peroxide compounds.